U.S. patent number 10,829,710 [Application Number 16/313,515] was granted by the patent office on 2020-11-10 for slipperiness-imparting agent and slipperiness-imparting method.
This patent grant is currently assigned to NOF CORPORATION, THE UNIVERSITY OF TOKYO. The grantee listed for this patent is NOF CORPORATION, THE UNIVERSITY OF TOKYO. Invention is credited to Kazuhiko Ishihara, Masaru Matsuda, Tomozumi Noda, Nobuyuki Sakamoto, Satoshi Yamada.
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United States Patent |
10,829,710 |
Ishihara , et al. |
November 10, 2020 |
Slipperiness-imparting agent and slipperiness-imparting method
Abstract
Provided is a lubricity-imparting agent that can impart durable
lubricity (in particular, lubricity at the time of wetting) to a
substrate. It has been found that a lubricity-imparting agent
including a copolymer containing a constitutional unit (A) based on
2-methacryloyloxyethyl phosphorylcholine and a constitutional unit
(B) based on a photoreactive functional group-containing monomer,
or a copolymer containing a constitutional unit (A) based on
2-methacryloyloxyethyl phosphorylcholine, a constitutional unit (B)
based on a photoreactive functional group-containing monomer, and a
constitutional unit (C) based on a hydrophobic group-containing
monomer can impart durable lubricity to a substrate surface through
a simple approach called photoirradiation.
Inventors: |
Ishihara; Kazuhiko (Tokyo,
JP), Noda; Tomozumi (Kawasaki, JP),
Matsuda; Masaru (Kawasaki, JP), Yamada; Satoshi
(Kawasaki, JP), Sakamoto; Nobuyuki (Kawasaki,
JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
NOF CORPORATION
THE UNIVERSITY OF TOKYO |
Tokyo
Tokyo |
N/A
N/A |
JP
JP |
|
|
Assignee: |
NOF CORPORATION (Tokyo,
JP)
THE UNIVERSITY OF TOKYO (Tokyo, JP)
|
Family
ID: |
1000005172306 |
Appl.
No.: |
16/313,515 |
Filed: |
June 28, 2017 |
PCT
Filed: |
June 28, 2017 |
PCT No.: |
PCT/JP2017/023655 |
371(c)(1),(2),(4) Date: |
December 27, 2018 |
PCT
Pub. No.: |
WO2018/003822 |
PCT
Pub. Date: |
January 04, 2018 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20190316054 A1 |
Oct 17, 2019 |
|
Foreign Application Priority Data
|
|
|
|
|
Jun 29, 2016 [JP] |
|
|
2016-129423 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F
230/02 (20130101); C10M 107/48 (20130101); C10M
2225/025 (20130101) |
Current International
Class: |
C10M
107/48 (20060101); C08F 230/02 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
2010-059346 |
|
Mar 2010 |
|
JP |
|
2010-059367 |
|
Mar 2010 |
|
JP |
|
2016-140259 |
|
Sep 2016 |
|
WO |
|
WO-2016140259 |
|
Sep 2016 |
|
WO |
|
Other References
Lin et al; Photoreactive Polymers Bearing a Zwitterionic
Phosphorylcholine Group for Surface Modification of Biomaterials;
ACS Applied Materials & Interfaces; vol. 7; pp. 17489-17498;
Published: Jul. 23, 2105. (Year: 2015). cited by examiner .
Konno T. et al., "Photo-immobilization of a phospholipid polymer
for surface modification", Biomaterials 26 (2005), pp. 1381-1388.
cited by applicant .
Extended European Search Report dated Jan. 15, 2020 from European
Patent Office in European Application No. 17820176.0. cited by
applicant.
|
Primary Examiner: Wieczorek; Michael P
Attorney, Agent or Firm: Sughrue Mion, PLLC
Claims
The invention claimed is:
1. A method of imparting lubricity to a substrate surface,
comprising the following steps (1) and (2): (1) a step of coating
the substrate surface with a copolymer having a weight-average
molecular weight of from 10,000 to 1,000,000, and (2) a step of
irradiating the substrate surface coated in the step (1) with light
to form a crosslinked body on the substrate surface, wherein the
copolymer contains 60 mol % to 99 mol % of a 2-methacryloyloxyethyl
phosphorylcholine constitutional unit (A) represented by the
following formula (1) and 1 mol % to 40 mol % of a photoreactive
functional group-containing constitutional unit (B) represented by
any one of the following formulae (2), (3), and (6): ##STR00055##
in the formula (2), R.sup.1 represents a hydrogen atom or a
hydroxyl group; ##STR00056## in the formula (3), R.sup.2 represents
the following formula (4) or the following formula (5);
##STR00057##
2. The method according to claim 1, wherein the constitutional unit
(B) comprises 4-methacryloyloxybenzophenone.
3. The method according to claim 1, wherein the constitutional unit
(B) comprises 4 methacryloxy-2-hydroxybenzophenone.
4. The method according to claim 1, wherein the constitutional unit
(B) is represented by formula (3) which is a copolymer containing
glycidyl methacrylate.
5. The method according to claim 1, wherein the constitutional unit
(B) comprises 4 (4 azidobenzoyloxymethyl)styrene.
6. A method of imparting lubricity to a substrate surface,
comprising the following steps (1) and (2): (1) a step of coating
the substrate surface with a copolymer having a weight-average
molecular weight of from 10,000 to 1,000,000, and (2) a step of
irradiating the substrate surface coated in the step (1) with light
to form a crosslinked body on the substrate surface, wherein the
copolymer contains 60 mol % to 98 mol % of a 2-methacryloyloxyethyl
phosphorylcholine constitutional unit (A) represented by the
following formula (1), 1 mol % to 39 mol % of a photoreactive
functional group-containing constitutional unit (B) represented by
any one of the following formulae (2), (3), and (6), and 1 mol % to
30 mol % of a hydrophobic group-containing constitutional unit (C)
represented by the following formula (7): ##STR00058## in the
formula (2), R.sup.1 represents a hydrogen atom or a hydroxyl
group; ##STR00059## in the formula (3), R.sup.2 represents the
following formula (4) or the following formula (5): ##STR00060## in
the formula (7), n represents an integer from 3 to 17.
7. The method according to claim 6, wherein the constitutional unit
(B) comprises 4 methacryloyloxybenzophenone, and the constitutional
unit (C) comprises butyl methacrylate.
8. The method according to claim 6, wherein the constitutional unit
(B) comprises 4 methacryloxy-2-hydroxybenzophenone, and the
constitutional unit (C) comprises butyl methacrylate.
9. The method according to claim 6, wherein the constitutional unit
(B) is represented by formula (3) which is a copolymer containing
glycidyl methacrylate, and the constitutional unit (C) comprises
butyl methacrylate.
10. The method according to claim 6, wherein the constitutional
unit (B) comprises 4 (4 azidobenzoyloxymethyl)styrene, and the
constitutional unit (C) comprises butyl methacrylate.
11. A crosslinked body, which is obtained by irradiating a
copolymer having a weight-average molecular weight of from 10,000
to 1,000,000, the copolymer containing 60 mol % to 99 mol % of a
2-methacryloyloxyethyl phosphorylcholine constitutional unit (A)
represented by the following formula (1) and 1 mol % to 40 mol % of
a photoreactive functional group-containing constitutional unit (B)
represented by any one of the following formulae (2), (3), and (6):
##STR00061## in the formula (2), R.sup.1 represents a hydrogen atom
or a hydroxyl group; ##STR00062## in the formula (3), R.sup.2
represents the following formula (4) or the following formula (5):
##STR00063##
12. A crosslinked body, which is obtained by irradiating a
copolymer having a weight-average molecular weight of from 10,000
to 1,000,000, the copolymer containing 60 mol % to 98 mol % of a
2-methacryloyloxyethyl phosphorylcholine constitutional unit (A)
represented by the following formula (1), 1 mol % to 39 mol % of a
photoreactive functional group-containing constitutional unit (B)
represented by any one of the following formulae (2), (3), and (6),
and 1 mol % to 30 mol % of a hydrophobic group-containing
constitutional unit (C) represented by the following formula (7):
##STR00064## in the formula (2), R.sup.1 represents a hydrogen atom
or a hydroxyl group; ##STR00065## in the formula (3), R.sup.2
represents the following formula (4) or the following formula (5);
##STR00066## in the formula (7), n represents an integer from 3 to
17.
13. An article, comprising the crosslinked body of claim 11.
14. An article, comprising the crosslinked body of claim 12.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
This Application is a National Stage of International Application
No. PCT/JP2017/023655 filed Jun. 28, 2017, claiming priority based
on Japanese Patent Application No. 2016-129423 filed Jun. 29, 2016
incorporated herein by reference.
TECHNICAL FIELD
The present invention relates to a lubricity-imparting agent
including a copolymer having at least a phosphorylcholine group
serving as a hydrophilic functional group and a photoreactive
functional group, and a lubricity-imparting method.
BACKGROUND ART
Many plastic products have been sold in a medical field. Examples
thereof include a catheter, a contact lens, an intraocular lens, a
cannula, and various tubes. Those medical devices are each attached
and detached in a state of being in contact with a biological
tissue, and hence the lubricity (in particular, lubricity at the
time of wetting) of the surface of each of the devices has been a
required item.
For example, there is a risk in that a contact lens that does not
have lubricity causes a reduction in wearing feeling at the time of
its wearing or causes damage to a tissue on the surface of an
eyeball, and there is a risk in that a catheter that does not have
lubricity involves pain or causes damage to a tissue at the time of
its insertion into a human body. Further, a medical device that
does not have lubricity imposes a heavy burden not only on a
patient but also on medical personnel required to perform delicate
work.
A method involving molding a medical device out of a fluorine-based
resin (Patent Literature 1), a method involving coating the medical
device with a hydrophilic copolymer, or the like has heretofore
been used as a technology for imparting lubricity to the medical
device. In particular, the method involving coating the medical
device with the hydrophilic copolymer is simple, and for example,
it has been known that the hydrophilic copolymer of Patent
Literature 2 containing a (meth)acrylate and vinyl alcohol, and the
hydrophilic copolymer of Patent Literature 3 containing
2-methacryloyloxyethyl phosphorylcholine each impart high lubricity
in addition to biocompatibility. However, many hydrophilic
copolymers have each involved a problem in terms of durability
because the copolymers are weakly bonded to substrate surfaces.
To solve the problem, in Patent Literature 4, there is a
description of a method involving fixing a hydrophilic copolymer
containing 2-methacryloyloxyethyl phosphorylcholine and various
reactive groups on a substrate surface. In the method, however, the
hydrophilic copolymer and a functional group on the substrate
surface are caused to react with each other by using a condensation
agent, such as 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide
hydrochloride, and hence a step of removing the condensation agent
and the hydrophilic copolymer that are unreacted after the reaction
has been required.
In Patent Literature 5, there is a description of a method
involving performing the graft polymerization of
2-methacryloyloxyethyl phosphorylcholine to a substrate having a
ketone group on its surface to form a copolymer layer. In the
method, however, the presence of a ketone group on the surface of
the substrate is required. In addition, the removal of unreacted
2-methacryloyloxyethyl phosphorylcholine after the graft
polymerization has been required.
In addition, in each of Patent Literature 6 and Patent Literature
7, there is a description of a copolymer of 2-methacryloyloxyethyl
phosphorylcholine and a photoreactive group-containing monomer in
order that the copolymer may be easily bonded to a substrate
surface. However, a photoreactive group-containing monomer that can
improve lubricity, the molecular weight of the copolymer, and the
like have not been described.
CITATION LIST
Patent Literature
[PTL 1] JP 2014-50549 A
[PTL 2] JP 2003-144541 A
[PTL 3] WO 2002/015911 A1
[PTL 4] JP 2000-226550 A
[PTL 5] WO 2011/021642 A1
[PTL 6] JP 2010-059346 A
[PTL 7] JP 2010-059367 A
SUMMARY OF INVENTION
Technical Problem
An object of the present invention is to provide a
lubricity-imparting agent that can impart durable lubricity (in
particular, lubricity at the time of wetting) to a substrate.
Solution to Problem
The inventors of the present invention have made extensive
investigations in view of the object, and as a result, have found
that a lubricity-imparting agent including a copolymer containing a
constitutional unit (A) based on 2-methacryloyloxyethyl
phosphorylcholine and a constitutional unit (B) based on a
photoreactive functional group-containing monomer, or a copolymer
containing a constitutional unit (A) based on
2-methacryloyloxyethyl phosphorylcholine, a constitutional unit (B)
based on a photoreactive functional group-containing monomer, and a
constitutional unit (C) based on a hydrophobic group-containing
monomer can impart durable lubricity to a substrate surface through
a simple approach called photoirradiation. Thus, the inventors have
completed the pre sent invention.
That is, the present invention includes the following.
[1] A lubricity-imparting agent, including 0.01 mass % to 5.0 mass
% of a copolymer having a weight-average molecular weight of from
10,000 to 1,000,000, the copolymer containing 60 mol % to 99 mol %
of a constitutional unit (A) based on 2-methacryloyloxyethyl
phosphorylcholine represented by the following formula (1) and 1
mol % to 40 mol % of a constitutional unit (B) based on a
photoreactive functional group-containing monomer represented by
any one of the following formulae (2), (3), and (6):
##STR00001##
##STR00002## in the formula (2), R.sup.1 represents a hydrogen atom
or a hydroxyl group;
##STR00003## in the formula (3), R.sup.2 represents the following
formula (4) or the following formula (5).
##STR00004##
[2] A lubricity-imparting agent, including 0.01 mass % to 5.0 mass
% of a copolymer having a weight-average molecular weight of from
10,000 to 1,000,000, the copolymer containing 60 mol % to 98 mol %
of a constitutional unit (A) based on 2-methacryloyloxyethyl
phosphorylcholine represented by the following formula (1), 1 mol %
to 39 mol % of a constitutional unit (B) based on a photoreactive
functional group-containing monomer represented by any one of the
following formulae (2), (3), and (6), and 1 mol % to 30 mol % of a
constitutional unit (C) based on a hydrophobic group-containing
monomer represented by the following formula (7):
##STR00005## in the formula (2), R.sup.1 represents a hydrogen atom
or a hydroxyl group;
##STR00006## in the formula (3), R.sup.2 represents the following
formula (4) or the following formula (5);
##STR00007## in the formula (7), n represents from 3 to 17.
[3] A lubricity-imparting agent according to the above-mentioned
item [1], wherein the constitutional unit (B) includes a
constitutional unit based on 4-methacryloyloxybenzophenone.
[4] A lubricity-imparting agent according to the above-mentioned
item [1], wherein the constitutional unit (B) includes a
constitutional unit based on
4-methacryloxy-2-hydroxybenzophenone.
[5] A lubricity-imparting agent according to the above-mentioned
item [2], wherein the constitutional unit (B) includes a
constitutional unit based on 4-methacryloyloxybenzophenone, and the
constitutional unit (C) includes a constitutional unit based on
butyl methacrylate.
[6] A lubricity-imparting agent according to the above-mentioned
item [2], wherein the constitutional unit (B) includes a
constitutional unit based on 4-methacryloxy-2-hydroxybenzophenone,
and the constitutional unit (C) includes a constitutional unit
based on butyl methacrylate.
[7] A lubricity-imparting agent according to the above-mentioned
item [2], wherein the constitutional unit (B) includes a
constitutional unit based on 4-methacryloyloxybenzophenone, and the
constitutional unit (C) includes a constitutional unit based on
stearyl methacrylate.
[8] A lubricity-imparting agent according to the above-mentioned
item [1], wherein the constitutional unit (B) includes a
constitutional unit based on glycidyl methacrylate.
[9] A lubricity-imparting agent according to the above-mentioned
item [2], wherein the constitutional unit (B) includes a
constitutional unit based on glycidyl methacrylate, and the
constitutional unit (C) includes a constitutional unit based on
butyl methacrylate.
[10] A lubricity-imparting agent according to the above-mentioned
item [2], wherein the constitutional unit (B) includes a
constitutional unit based on glycidyl methacrylate, and the
constitutional unit (C) includes a constitutional unit based on
stearyl methacrylate.
[11] A lubricity-imparting agent according to the above-mentioned
item [1], wherein the constitutional unit (B) includes a
constitutional unit based on
4-(4-azidobenzoyloxymethyl)styrene.
[12] A lubricity-imparting agent according to the above-mentioned
item [2], wherein the constitutional unit (B) includes a
constitutional unit based on 4-(4-azidobenzoyloxymethyl)styrene,
and the constitutional unit (C) includes a constitutional unit
based on butyl methacrylate.
[13] A lubricity-imparting agent according to the above-mentioned
item [2], wherein the constitutional unit (B) includes a
constitutional unit based on 4-(4-azidobenzoyloxymethyl)styrene,
and the constitutional unit (C) includes a constitutional unit
based on stearyl methacrylate.
[14] A method of imparting lubricity to a substrate surface,
including the following steps (1) and (2):
(1) a step of coating the substrate surface with the
lubricity-imparting agent of any one of the above-mentioned items
[1] to [13]; and
(2) a step of irradiating the substrate surface coated in the step
(1) with light to form a crosslinked body on the substrate
surface.
[15] A method of forming a crosslinked body, including: coating a
substrate surface with the lubricity-imparting agent of any one of
the above-mentioned items [1] to [13]; and
then irradiating the substrate surface with light to form the
crosslinked body on the substrate surface.
[16] A crosslinked body, which is obtained by the method of forming
a crosslinked body of the above-mentioned item [15].
[17] A crosslinked body, which is obtained by irradiating the
lubricity-imparting agent of any one of the above-mentioned items
[1] to [13] with light.
[18] An article, including the crosslinked body of the
above-mentioned item [16] or [17].
[19] A lubricity-imparting method, including using a copolymer
having a weight-average molecular weight of from 10,000 to
1,000,000, the copolymer containing 60 mol % to 99 mol % of a
constitutional unit (A) based on 2-methacryloyloxyethyl
phosphorylcholine represented by the following formula (1) and 1
mol % to 40 mol % of a constitutional unit (B) based on a
photoreactive functional group-containing monomer represented by
any one of the following formulae (2), (3), and (6):
##STR00008## in the formula (2), R.sup.1 represents a hydrogen atom
or a hydroxyl group;
##STR00009## in the formula (3), R.sup.2 represents the following
formula (4) or the following formula (5).
##STR00010##
[20] A lubricity-imparting method, including using a copolymer
having a weight-average molecular weight of from 10,000 to
1,000,000, the copolymer containing 60 mol % to 98 mol % of a
constitutional unit (A) based on 2-methacryloyloxyethyl
phosphorylcholine represented by the following formula (1), 1 mol %
to 39 mol % of a constitutional unit (B) based on a photoreactive
functional group-containing monomer represented by any one of the
following formulae (2), (3), and (6), and 1 mol % to 30 mol % of a
constitutional unit (C) based on a hydrophobic group-containing
monomer represented by the following formula (7):
##STR00011## in the formula (2), R.sup.1 represents a hydrogen atom
or a hydroxyl group;
##STR00012## in the formula (3), R.sup.2 represents the following
formula (4) or the following formula (5);
##STR00013## in the formula (7), n represents from 3 to 17.
[21] A lubricity-imparting copolymer having a weight-average
molecular weight of from 10,000 to 1,000,000, the copolymer
containing 60 mol % to 99 mol % of a constitutional unit (A) based
on 2-methacryloyloxyethyl phosphorylcholine represented by the
following formula (1) and 1 mol % to 40 mol % of a constitutional
unit (B) based on a photoreactive functional group-containing
monomer represented by any one of the following formulae (2), (3),
and (6):
##STR00014## in the formula (2), R.sup.1 represents a hydrogen atom
or a hydroxyl group;
##STR00015## in the formula (3), R.sup.2 represents the following
formula (4) or the following formula (5).
##STR00016##
[22] A lubricity-imparting copolymer having a weight-average
molecular weight of from 10,000 to 1,000,000, the copolymer
containing 60 mol % to 98 mol % of a constitutional unit (A) based
on 2-methacryloyloxyethyl phosphorylcholine represented by the
following formula (1), 1 mol % to 39 mol % of a constitutional unit
(B) based on a photoreactive functional group-containing monomer
represented by any one of the following formulae (2), (3), and (6),
and 1 mol % to 30 mol % of a constitutional unit (C) based on a
hydrophobic group-containing monomer represented by the following
formula (7):
##STR00017## in the formula (2), R.sup.1 represents a hydrogen atom
or a hydroxyl group;
##STR00018## in the formula (3), R.sup.2 represents the following
formula (4) or the following formula (5);
##STR00019## in the formula (7), n represents from 3 to 17.
[23] A use of a copolymer having a weight-average molecular weight
of from 10,000 to 1,000,000, the copolymer containing 60 mol % to
99 mol % of a constitutional unit (A) based on
2-methacryloyloxyethyl phosphorylcholine represented by the
following formula (1) and 1 mol % to 40 mol % of a constitutional
unit (B) based on a photoreactive functional group-containing
monomer represented by any one of the following formulae (2), (3),
and (6), in production of a lubricity-imparting agent:
##STR00020## in the formula (2), R.sup.1 represents a hydrogen atom
or a hydroxyl group;
##STR00021## in the formula (3), R.sup.2 represents the following
formula (4) or the following formula (5).
##STR00022##
[24] A use of a copolymer having a weight-average molecular weight
of from 10,000 to 1,000,000, the copolymer containing 60 mol % to
98 mol % of a constitutional unit (A) based on
2-methacryloyloxyethyl phosphorylcholine represented by the
following formula (1), 1 mol % to 39 mol % of a constitutional unit
(B) based on a photoreactive functional group-containing monomer
represented by any one of the following formulae (2), (3), and (6),
and 1 mol % to 30 mol % of a constitutional unit (C) based on a
hydrophobic group-containing monomer represented by the following
formula (7), in production of a lubricity-imparting agent:
##STR00023## in the formula (2), R.sup.1 represents a hydrogen atom
or a hydroxyl group;
##STR00024## in the formula (3), R.sup.2 represents the following
formula (4) or the following formula (5);
##STR00025## in the formula (7), n represents from 3 to 17.
Advantageous Effects of Invention
The lubricity-imparting agent of the present invention can impart
durable lubricity to a substrate surface. In addition, the article
of the present invention has highly durable lubricity.
DESCRIPTION OF EMBODIMENTS
An embodiment of the present invention is described in detail
below.
A lubricity-imparting agent of the present invention includes a
copolymer containing a constitutional unit (A) based on
2-methacryloyloxyethyl phosphorylcholine and a constitutional unit
(B) based on a photoreactive functional group-containing monomer,
or a copolymer containing a constitutional unit (A) based on
2-methacryloyloxyethyl phosphorylcholine, a constitutional unit (B)
based on a photoreactive functional group-containing monomer, and a
constitutional unit (C) based on a hydrophobic group-containing
monomer. The constitutional units based on the respective monomers
are described below.
[Constitutional Unit (A) Based on 2-Methacryloyloxyethyl
Phosphorylcholine]
The copolymer in the lubricity-imparting agent of the present
invention contains the constitutional unit (A) based on
2-methacryloyloxyethyl phosphorylcholine represented by the
following formula (1). In the constitutional unit (A), a
phosphorylcholine group is a polar group having the same structure
as that of a phospholipid serving as a main component of a
biological membrane. The introduction of the constitutional unit
(A) having a phosphorylcholine group into the copolymer can impart
not only lubricity but also biocompatibility, such as a protein
adsorption-suppressing effect, a cell adsorption-suppressing
effect, antithrombogenicity, or hydrophilicity, to the
copolymer.
An example of the phosphorylcholine group-containing monomer is
2-(meth)acryloyloxyethyl-2'-(trimethylammonio)ethylphosphate (also
known as: 2-methacryloyloxyethyl-2-trimethylammonioethyl
phosphate).
##STR00026##
[Constitutional Unit (B) Based on Photoreactive Functional
Group-Containing Monomer]
The copolymer in the lubricity-imparting agent of the present
invention contains the constitutional unit (B) based on a
photoreactive functional group-containing monomer. A constitutional
unit based on a benzophenone group-containing monomer represented
by the following formula (2), or a constitutional unit based on an
azidophenyl group-containing monomer represented by the following
formula (3) or (6) is given as the constitutional unit (B) based on
a photoreactive functional group-containing monomer.
##STR00027##
In the formula (2), R.sup.1 represents a hydrogen atom or a
hydroxyl group.
##STR00028##
In the formula (3), R.sup.2 represents the following formula (4) or
the following formula (5).
##STR00029##
A benzophenone group is brought into a triplet excited state rich
in reactivity by photoirradiation, and can be bonded to a substrate
or a copolymer by abstracting a hydrogen atom therefrom. Examples
of the benzophenone group-containing monomer include, but not
particularly limited to, 4-methacryloyloxybenzophenone (MBP) and
4-methacryloxy-2-hydroxybenzophenone (MHP).
The azidophenyl group produces a nitrene rich in reactivity through
photoirradiation, and can be bonded to a substrate or a copolymer
by abstracting a hydrogen atom therefrom.
With regard to the constitutional unit based on an azidophenyl
group-containing monomer represented by the formula (3), when a
copolymer containing glycidyl methacrylate (hereinafter abbreviated
as "GMA") represented by the following formula (9) is polymerized,
and then 4-azidobenzoic acid (hereinafter abbreviated as "ABA")
represented by the following formula (10) is caused to undergo a
ring-opening esterification reaction with a glycidyl group of GMA
in the presence of triethylamine, a copolymer containing a
constitutional unit based on a GMA monomer containing an
azidophenyl group (hereinafter abbreviated as "GMA-Az") may be
obtained.
The constitutional unit based on an azidophenyl group-containing
monomer represented by the formula (6) may be obtained from
4-(4-azidobenzoyloxymethyl)styrene (AzSt) represented by the
following formula (8) that may be synthesized by a substitution
reaction between chloromethylstyrene (hereinafter abbreviated as
"CMS") represented by the following formula (11) and an alkali
metal carboxylate represented by the following formula (12). The
alkali metal carboxylate is prepared from ABA and an alkali metal
salt, and in the formula (12), M represents an alkali metal, such
as a lithium atom, a sodium atom, or a potassium atom, preferably a
sodium atom or a potassium atom.
##STR00030##
In the formula (12), M represents an alkali metal.
[Constitutional Unit (C) Based on Hydrophobic Group-Containing
Monomer]
The copolymer in the lubricity-imparting agent of the present
invention may contain the constitutional unit (C) based on a
hydrophobic group-containing monomer represented by the formula (7)
in its copolymer structure. A hydrophobic group can improve the
applicability of the copolymer through its physical adsorption to a
hydrophobic substrate surface.
Examples of the hydrophobic group-containing monomer include, but
not particularly limited to, methacrylic acid esters each having a
hydrophobic substituent, such as butyl (meth)acrylate, hexyl
(meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate,
dodecyl (meth)acrylate, tridecyl (meth)acrylate, and stearyl
(meth)acrylate.
##STR00031##
In the formula (7), n represents from 3 to 17.
[Lubricity-Imparting Agent]
The lubricity-imparting agent of the present invention includes the
copolymer containing the constitutional unit (A) based on
2-methacryloyloxyethyl phosphorylcholine and the constitutional
unit (B) based on a photoreactive functional group-containing
monomer, or the copolymer containing the constitutional unit (A)
based on 2-methacryloyloxyethyl phosphorylcholine, the
constitutional unit (B) based on a photoreactive functional
group-containing monomer, and the constitutional unit (C) based on
a hydrophobic group-containing monomer at a concentration of from
0.01 mass % to 5.0 mass %, preferably from 0.01 mass % to 2.5 mass
%, more preferably from 0.1 mass % to 1.0 mass %.
The copolymer to be incorporated into the lubricity-imparting agent
of the present invention is a copolymer containing 60 mol % to 99
mol % of the constitutional unit (A) based on
2-methacryloyloxyethyl phosphorylcholine and 1 mol % to 40 mol % of
the constitutional unit (B) based on a photoreactive functional
group-containing monomer, or a copolymer containing 60 mol % to mol
% of the constitutional unit (A) based on 2-methacryloyloxyethyl
phosphorylcholine, 1 mol % to 39 mol % of the constitutional unit
(B) based on a photoreactive functional group-containing monomer,
and 1 mol % to 30 mol % of the constitutional unit (C) based on a
hydrophobic group-containing monomer.
The weight-average molecular weight of the copolymer to be
incorporated into the lubricity-imparting agent of the present
invention falls within the range of from 10,000 to 1,000,000,
preferably from 15,000 to 750,000, more preferably from 25,000 to
520,000 in terms of the exhibition of satisfactory lubricity.
The lubricity-imparting agent of the present invention is not
particularly limited as long as the agent includes the copolymer as
an effective component, and the agent may include a solvent for
dissolving the copolymer. A lower alcohol, such as ethanol,
methanol, normal propanol, or isopropanol, purified water, pure
water, ultrapure water, ion-exchanged water, physiological saline,
or a buffer, such as a phosphate buffer, a Tris-hydrochloric acid
buffer, or a HEPES buffer, or a product obtained by mixing two or
more of these solvents at an arbitrary ratio may be used as the
solvent for dissolving the copolymer.
The lubricity-imparting agent of the present invention includes
0.01 mass % to 5.0 mass %, preferably 0.01 mass % to 2.5 mass %,
more preferably 0.1 mass % to 1.0 mass % of the copolymer. When the
content is excessively high, the agent cannot be uniformly applied,
and when the content is excessively low, an effective
lubricity-improving effect is not obtained.
The lubricity-imparting agent of the present invention may contain,
in addition to the copolymer, a lower alcohol, water, a buffer, or
the like, and may be further blended with, as required, an
antiseptic agent (e.g., sodium benzoate, sodium salicylate,
potassium sorbate, or benzalkonium chloride), a surfactant (e.g.,
polysorbate 80, sorbitan monooleate, squalane, or sodium lauryl
sulfate), a hydrophilic copolymer (e.g., polyethylene glycol or
polyvinyl alcohol), a humectant (e.g., concentrated glycerin,
methyl cellulose, hyaluronic acid, a 2-methacryloyloxyethyl
phosphorylcholine polymer, a 2-methacryloyloxyethyl
phosphorylcholine-butyl methacrylate copolymer liquid, or liquid
paraffin), an amino acid (e.g., L-ascorbic acid, alanine,
L-glutamic acid, or L-methionine), a medicinal component (e.g.,
indomethacin or dexamethasone), a blood anticoagulant (e.g.,
heparin, sodium citrate, ethylenediaminetetraacetic acid,
acetylsalicylic acid, urokinase, or warfarin), an anticancer agent
(e.g., taxol, leustatin, adriacin, bleomycin, or imatinib), an
antibiotic (e.g., kanamycin, streptomycin, or polymyxin B), an
absorption promoter (e.g., sodium caprate), a stabilizing agent
(e.g., calcium citrate, natural vitamin E, human serum albumin, or
dextran), a radiation absorber (e.g., a metal, such as barium,
silver, tin, platinum, gold, or zirconium, and a compound, such as
a sulfate, a carbonate, or a nitrate, containing any of those
metals), and various compounds other than the above-mentioned
compounds.
[Polymerization Reaction of Copolymer]
The polymerization reaction of the copolymer in the
lubricity-imparting agent of the present invention may be performed
by a known method, such as radical polymerization, such as bulk
polymerization, suspension polymerization, emulsion polymerization,
or solution polymerization, in the presence of a radical
polymerization initiator, such as a peroxide or an azo compound,
after the inside of a reaction system has been purged with an inert
gas, such as nitrogen, carbon dioxide, argon, or helium, or in the
inert gas atmosphere.
The polymerization reaction is preferably the solution
polymerization from the viewpoint of, for example, the purification
of the polymer to be obtained. Those polymerization reactions
provide copolymers having constitutional units represented by the
following formulae (13) to (18).
"a", "b", and "c" merely represent the constituent ratios of the
constitutional units, and the copolymer may be of any one of the
following structures: a random copolymer, a block copolymer, and a
graft copolymer, and a combination of two or more thereof.
In each of the copolymers represented by the formulae (13) to (15),
"a" and "b" (molar ratios) satisfy relationships of a/(a+b)=0.60 to
0.99 and b/(a+b)=0.01 to 0.40. In each of the copolymers
represented by the formulae (16) to (18), "a", "b", and "c" satisfy
relationships of a/(a+b+c)=0.60 to 0.98, b/(a+b+c)=0.01 to 0.39,
and c/(a+b+c)=0.01 to 0.30.
As another representation, in each of the copolymers represented by
the formulae (13) to (15), the ratio "a" of the phosphorylcholine
constitutional unit (A) of the copolymer of the present invention
and the ratio "b" of the constitutional unit (B) based on a
photoreactive functional group-containing monomer thereof satisfy a
ratio "a:b" of 100:1 to 67.
In addition, in each of the copolymers represented by the formulae
(16) to (18), the ratio "a" of the phosphorylcholine constitutional
unit (A) of the copolymer of the present invention, the ratio "b"
of the constitutional unit (B) based on a photoreactive functional
group-containing monomer thereof, and the ratio "c" of the
constitutional unit (C) based on a hydrophobic group-containing
monomer thereof satisfy a ratio "a:b:c" of 100:1 to 65:1 to 50.
Further, as can be seen from Examples below, the ratio "a" of the
phosphorylcholine constitutional unit (A) of the copolymer of the
present invention, the ratio "b" of the constitutional unit (B)
based on a photoreactive functional group-containing monomer
thereof, and the ratio "c" of the constitutional unit (C) based on
a hydrophobic group-containing monomer thereof more preferably
satisfy a ratio "a:b:c" of 0.6 to 0.8:0.05 to 0.1:0.1 to 0.3
(Examples 12, 16, 19, 21, and 23).
##STR00032##
In the formula (13), R.sup.1 represents a hydrogen atom or a
hydroxyl group.
##STR00033##
In the formula (14), R.sup.2 represents the following formula (4)
or (5).
##STR00034##
In the formula (16), R.sup.1 represents a hydrogen atom or a
hydroxyl group, and n represents from 3 to 17.
##STR00035##
In the formula (17), R.sup.2 represents the formula (4) or (5), and
n represents from 3 to 17.
##STR00036##
In the formula (18), n represents from 3 to 17.
A constitutional unit except the constitutional unit (A) based on
2-methacryloyloxyethyl phosphorylcholine, the constitutional unit
(B) based on a photoreactive functional group-containing monomer,
and the constitutional unit (C) based on a hydrophobic
group-containing monomer may be incorporated into the copolymer to
the extent that the lubricity-improving action of the
lubricity-imparting agent is not adversely affected.
Examples thereof may include constitutional units based on a linear
or branched alkyl (meth)acrylate, a cyclic alkyl (meth)acrylate, an
aromatic group-containing (meth)acrylate, a styrene-based monomer,
a vinyl ether monomer, a vinyl ester monomer, a hydrophilic
hydroxyl group-containing (meth)acrylate, an acid group-containing
monomer, a nitrogen-containing group-containing monomer, an amino
group-containing monomer, and a cationic group-containing
monomer.
Examples of the linear or branched alkyl (meth)acrylate include
methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate,
and 2-ethylhexyl (meth)acrylate.
An example of the cyclic alkyl (meth)acrylate is cyclohexyl
(meth)acrylate.
Examples of the aromatic group-containing (meth)acrylate include
benzyl (meth)acrylate and phenoxyethyl (meth)acrylate.
Examples of the styrene-based monomer include styrene,
methylstyrene, and chloromethylstyrene.
Examples of the vinyl ether monomer include methyl vinyl ether and
butyl vinyl ether.
Examples of the vinyl ester monomer include vinyl acetate and vinyl
propionate.
Examples of the hydrophilic hydroxyl group-containing
(meth)acrylate include polyethylene glycol (meth)acrylate,
polypropylene glycol (meth)acrylate, 2-hydroxyethyl (meth)acrylate,
2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl
(meth)acrylate.
Examples of the acid group-containing monomer include (meth)acrylic
acid, styrenesulfonic acid, and (meth)acryloyloxyphosphonic
acid.
An example of the nitrogen-containing group-containing monomer is
N-vinylpyrrolidone.
Examples of the amino group-containing monomer include aminoethyl
(meth)acrylate, dimethylamino (meth)acrylate, and
N,N-dimethylaminopropyl (meth)acrylamide.
An example of the cationic group-containing monomer is
2-hydroxy-3-(meth)acryloyloxypropyltrimethylammonium chloride.
<Lubricity-Imparting Method>
A lubricity-imparting method including using the
lubricity-imparting agent of the present invention is
described.
First, the lubricity-imparting agent of the present invention can
be used in plastic, metal, and silicone articles (e.g., a guide
wire, a stent, an artificial joint, and a silicone tube), in
particular, the plastic articles. The plastic articles are, for
example, articles formed from polystyrene, polyethylene,
polypropylene, polyethylene terephthalate, polyolefin, polyether
ether ketone, polyurethane, and polycarbonate, and are particularly
preferably, for example, a catheter, a guide wire (whose surface is
covered with a plastic), a contact lens, and an intraocular lens.
When the surface of any such plastic article is treated with the
lubricity-imparting agent of the present invention, the lubricity
of the surface can be improved and the lubricity has durability.
More specifically, an article in which the lubricity-imparting
agent of the present invention is used is preferably an article
from which a hydrogen atom can be abstracted, such as a plastic
material, but the use of an appropriate binder enables the agent to
be used in an article except the plastic articles.
Next, a method of coating the surface of a substrate with the
lubricity-imparting agent of the present invention is described. A
spin coating method, a spray coating method, a cast coating method,
a dip coating method, a roll coating method, a flow coating method,
or the like may be used as the method of coating the surface with
the lubricity-imparting agent of the present invention, but the dip
coating method or the cast coating method is preferred. Further,
after the coating, the agent may be dried as required at room
temperature or by being warmed.
The substrate coated with (having applied thereto) the
lubricity-imparting agent of the present invention is irradiated
with light having a wavelength of from 200 nm to 400 nm, preferably
light having a wavelength of from 254 nm to 365 nm. Further, an
excess lubricity-imparting agent may be washed off by washing the
substrate with a proper solvent, such as pure water, ethanol, or
methanol, after the photoirradiation.
Lubricity can be imparted to an article (in particular, a plastic
article) by such lubricity-imparting method as described above.
<Method of Forming Crosslinked Body, Crosslinked Body, and
Article>
A method of forming a crosslinked body of the present invention
includes: coating a substrate surface with the lubricity-imparting
agent of the present invention; and then irradiating the substrate
surface with light to form the crosslinked body on the substrate
surface.
A crosslinked body of the present invention may be obtained by the
method of forming a crosslinked body of the present invention.
Alternatively, the crosslinked body may be obtained by irradiating
the lubricity-imparting agent of the present invention with
light.
An article of the present invention includes the crosslinked body
of the present invention.
The combination of the constitutional unit (A) based on
2-methacryloyloxyethyl phosphorylcholine of the copolymer of the
present invention, the constitutional unit (B) based on a
photoreactive functional group-containing monomer thereof, and the
constitutional unit (C) based on a hydrophobic group-containing
monomer thereof is as described below, but is not particularly
limited (the left portion represents the constitutional unit (A),
the central portion represents the constitutional unit (B), and the
right portion represents the constitutional unit (C)).
MPC-MBP
MPC-MBP-butyl methacrylate
MPC-MBP-hexyl methacrylate
MPC-MBP-2-ethylhexyl methacrylate
MPC-MBP-decyl methacrylate
MPC-MBP-dodecyl methacrylate
MPC-MBP-tridecyl methacrylate
MPC-MBP-stearyl methacrylate
MPC-MHP
MPC-MHP-butyl methacrylate
MPC-MHP-hexyl methacrylate
MPC-MHP-2-ethylhexyl methacrylate
MPC-MHP-decyl methacrylate
MPC-MHP-dodecyl methacrylate
MPC-MHP-tridecyl methacrylate
MPC-MHP-stearyl methacrylate
MPC-GMA-Az
MPC-GMA-Az-butyl methacrylate
MPC-GMA-Az-hexyl methacrylate
MPC-GMA-Az-2-ethylhexyl methacrylate
MPC-GMA-Az-decyl methacrylate
MPC-GMA-Az-dodecyl methacrylate
MPC-GMA-Az-tridecyl methacrylate
MPC-GMA-Az-stearyl methacrylate
MPC-Az St
MPC-AzSt-butyl methacrylate
MPC-AzSt-hexyl methacrylate
MPC-AzSt-2-ethylhexyl methacrylate
MPC-AzSt-decyl methacrylate
MPC-AzSt-dodecyl methacrylate
MPC-AzSt-tridecyl methacrylate
MPC-AzSt-stearyl methacrylate
Further, as can be seen from Examples below, more preferred
combinations of the phosphorylcholine constitutional unit,
photoreactive constitutional unit, and hydrophobic constitutional
unit of the copolymer of the present invention are MPC-GMA-Az-butyl
methacrylate (Example 12), MPC-GMA-Az-stearyl methacrylate (Example
16), MPC-AzSt-butyl methacrylate (Polymerization Example 19 and
Polymerization Example 21), and MPC-AzSt-stearyl methacrylate
(Polymerization Example 23).
Accordingly, GMA-Az and AzSt are each particularly preferred as the
photoreactive constitutional unit of the copolymer of the present
invention.
The present invention is also directed to a lubricity-imparting
method, including using a copolymer having a weight-average
molecular weight of from 10,000 to 1,000,000, the copolymer
containing 60 mol % to 99 mol % of a constitutional unit (A) based
on 2-methacryloyloxyethyl phosphorylcholine represented by the
following formula (1) and 1 mol % to 40 mol % of a constitutional
unit (B) based on a photoreactive functional group-containing
monomer represented by any one of the following formulae (2), (3),
and (6):
##STR00037##
In the formula (2), R.sup.1 represents a hydrogen atom or a
hydroxyl group.
##STR00038##
In the formula (3), R.sup.2 represents the following formula (4) or
the following formula (5).
##STR00039##
The present invention is also directed to a lubricity-imparting
method, including using a copolymer having a weight-average
molecular weight of from 10,000 to 1,000,000, the copolymer
containing 60 mol % to 98 mol % of a constitutional unit (A) based
on 2-methacryloyloxyethyl phosphorylcholine represented by the
following formula (1), 1 mol % to 39 mol % of a constitutional unit
(B) based on a photoreactive functional group-containing monomer
represented by any one of the following formulae (2), (3), and (6),
and 1 mol % to 30 mol % of a constitutional unit (C) based on a
hydrophobic group-containing monomer represented by the following
formula (7):
##STR00040##
In the formula (2), R.sup.1 represents a hydrogen atom or a
hydroxyl group.
##STR00041##
In the formula (3), R.sup.2 represents the following formula (4) or
the following formula (5).
##STR00042##
In the formula (7), n represents from 3 to 17.
The present invention is also directed to a lubricity-imparting
copolymer having a weight-average molecular weight of from 10,000
to 1,000,000, the copolymer containing 60 mol % to 99 mol % of a
constitutional unit (A) based on 2-methacryloyloxyethyl
phosphorylcholine represented by the following formula (1) and 1
mol % to 40 mol % of a constitutional unit (B) based on a
photoreactive functional group-containing monomer represented by
any one of the following formulae (2), (3), and (6):
##STR00043##
In the formula (2), R.sup.1 represents a hydrogen atom or a
hydroxyl group.
##STR00044##
In the formula (3), R.sup.2 represents the following formula (4) or
the following formula (5).
##STR00045##
The present invention is also directed to a lubricity-imparting
copolymer having a weight-average molecular weight of from 10,000
to 1,000,000, the copolymer containing 60 mol % to 98 mol % of a
constitutional unit (A) based on 2-methacryloyloxyethyl
phosphorylcholine represented by the following formula (1), 1 mol %
to 39 mol % of a constitutional unit (B) based on a photoreactive
functional group-containing monomer represented by any one of the
following formulae (2), (3), and (6), and 1 mol % to 30 mol % of a
constitutional unit (C) based on a hydrophobic group-containing
monomer represented by the following formula (7):
##STR00046##
In the formula (2), R.sup.1 represents a hydrogen atom or a
hydroxyl group.
##STR00047##
In the formula (3), R.sup.2 represents the following formula (4) or
the following formula (5).
##STR00048##
In the formula (7), n represents from 3 to 17.
The present invention is also directed to a use of a copolymer
having a weight-average molecular weight of from 10,000 to
1,000,000, the copolymer containing 60 mol % to 99 mol % of a
constitutional unit (A) based on 2-methacryloyloxyethyl
phosphorylcholine represented by the following formula (1) and 1
mol % to 40 mol % of a constitutional unit (B) based on a
photoreactive functional group-containing monomer represented by
any one of the following formulae (2), (3), and(6), in production
of a lubricity-imparting agent:
##STR00049##
In the formula (2), R.sup.1 represents a hydrogen atom or a
hydroxyl group.
##STR00050##
In the formula (3), R.sup.2 represents the following formula (4) or
the following formula (5).
##STR00051##
The present invention is also directed to a use of a copolymer
having a weight-average molecular weight of from 10,000 to
1,000,000, the copolymer containing 60 mol % to 98 mol % of a
constitutional unit (A) based on 2-methacryloyloxyethyl
phosphorylcholine represented by the following formula (1), 1 mol %
to 39 mol % of a constitutional unit (B) based on a photoreactive
functional group-containing monomer represented by any one of the
following formulae (2), (3), and (6), and 1 mol % to 30 mol % of a
constitutional unit (C) based on a hydrophobic group-containing
monomer represented by the following formula (7), in production of
a lubricity-imparting agent:
##STR00052##
In the formula (2), R.sup.1 represents a hydrogen atom or a
hydroxyl group.
##STR00053##
In the formula (3), R.sup.2 represents the following formula (4) or
the following formula (5).
##STR00054##
In the formula (7), n represents from 3 to 17.
EXAMPLES
The present invention is described in more detail below by way of
Examples and Comparative Examples.
<Addition of Azidobenzoic Acid to Glycidyl Methacrylate
(Addition of ABA to Copolymer)>
Copolymers each containing glycidyl methacrylate (GMA) were
polymerized under polymerization conditions shown in Table land
Table 2 to be described later. After that, 1.5 molar equivalents of
azidobenzoic acid (ABA) with respect to GMA were dissolved in each
of solution containing the copolymers, and the temperature of the
solution was increased to 80.degree. C. After that, 0.2 molar
equivalent of triethylamine (TEA) with respect to GMA was added to
the solution, and a reaction was performed for 48 hours to provide
a copolymer containing a constitutional unit (GMA-Az) based on a
GMA monomer containing an azidophenyl group.
<Synthesis of 4-(4-Azidobenzoyloxymethyl)styrene (AzSt)
(Synthesis of Monomer from which Constitutional Unit (B)
Represented by Formula (6) is Derived)>
6.42 g of azidobenzoic acid and 64 g of dimethylsulfoxide were
weighed in a 200-milliliter recovery flask, and a temperature in
the flask was increased to 50.degree. C. to dissolve the materials.
2.72 g of potassium carbonate was added to the solution, and the
mixture was stirred for 30 minutes. After a lapse of time, 5.46 g
of chloromethylstyrene was added to the mixture, and a reaction was
performed for 8 hours. After a lapse of 8 hours, 193.15 g of ethyl
acetate was added to the resultant, and the organic layer was
washed with 63.95 g of saturated saline five times, and was
separated and extracted. The organic layer was dehydrated with
sodium sulfate, and was then concentrated. The residue was
dissolved in ethyl acetate so that the concentration of AzSt thus
obtained became 50 mass %.
Various measurements in Polymerization Examples were performed in
accordance with the following methods.
<Measurement of Weight-Average Molecular Weight>
5 mg of the resultant copolymer is dissolved in 1 g of a 0.1 mol/L
aqueous solution of sodium sulfate, and its weight-average
molecular weight is measured by gel permeation chromatography
(GPC). Measurement conditions are as described below.
Apparatus: RI-8020, DP-8020, SD-8022, and AS-8020 (manufactured by
Tosoh Corporation), and 865-CO (manufactured by JASCO Corporation),
column: Shodex OHpak (manufactured by Showa Denko K.K.), mobile
phase: a 0.1 mol/L aqueous solution of sodium sulfate, standard
substance: pullulan, detection: a differential refractometer,
calculation of weight-average molecular weight (Mw): a molecular
weight calculation program (GPC program for SC-8020), flow rate:
1.0 mL/min, column temperature: 40.degree. C., sample solution
injection amount: 100 .mu.L, measurement time: 30 minutes.
Polymerization Examples 1 to 8
Polymerization was performed in accordance with copolymer
composition ratios and polymerization conditions (at 65.degree. C.
for 6 hours or at 60.degree. C. for 6 hours) shown in Table 1, and
purification by precipitation, .sup.1H-NMR analysis, and
weight-average molecular weight measurement were performed. The
results of the weight-average molecular weight measurement are
shown in Table 1.
Polymerization Examples 9 to 16
Polymerization was performed in accordance with copolymer
composition ratios and polymerization conditions (at 60.degree. C.
for 4 hours and then at 70.degree. C. for 2 hours) shown in Tables
1 and 2, and ABA was added to GMA in each of the resultant
copolymers (at 80.degree. C. for 48 hours), followed by the
performance of purification by precipitation, .sup.1H-NMR analysis,
and weight-average molecular weight measurement. The results of the
weight-average molecular weight measurement are shown in Tables 1
and 2.
Polymerization Examples 17 to 23
Polymerization was performed in accordance with copolymer
composition ratios and polymerization conditions (at 60.degree. C.
for 4 hours and then at 70.degree. C. for 2 hours) shown in Table
2, and purification by precipitation, .sup.1H-NMR analysis, and
weight-average molecular weight measurement were performed. The
results of the weight-average molecular weight measurement are
shown in Table 2.
Comparative Polymerization Examples 1 to 4
Polymerization was performed in accordance with copolymer
composition ratios and polymerization conditions shown in Table 2,
followed by the performance of purification by precipitation,
.sup.1H-NMR analysis, and weight-average molecular weight
measurement. The results of the weight-average molecular weight
measurement are shown in Table 2.
Details about the materials used in the polymerization of the
copolymers in Polymerization Examples and Comparative
Polymerization Examples are described below (the materials are
shown in abbreviations in tables).
MPC: 2-methacryloyloxyethyl phosphorylcholine
MBP: 4-methacryloyloxybenzophenone
MHP: 4-methacryloxy-2-hydroxybenzophenone
GMA: glycidyl methacrylate
BMA: butyl methacrylate
SMA: stearyl methacrylate
AzSt: 4-(4-azido-benzoyloxymethyl)styrene (50 mass % ethyl acetate
solution product)
AEMA: aminoethyl methacrylate
ABA: azidobenzoic acid
TEA: triethylamine
EtOH: ethanol
nPA: n-propanol
PW: water (pure water)
AIBN: 2,2-azobisisobutyronitrile
<Evaluation of Lubricity-Imparting Effect>
The copolymers (Polymerization Examples 1 to 23) in the
lubricity-imparting agent of the present invention, and analogs
thereof (Comparative Polymerization Examples 1 to 4) were evaluated
for their lubricity-imparting effects.
A lubricity-imparting agent including each copolymer was dissolved
in a solvent so that its concentration became a predetermined
value. A plate made of polyethylene terephthalate was immersed in
the solution for 30 seconds or more. Ethanol (EtOH) or a 50 wt %
aqueous solution of ethanol (EtOH/PW) was used as the solvent. The
plate was irradiated with light having a wavelength of 254 nm, and
an unreacted lubricity-imparting agent was washed off with the
solvent, followed by the measurement of the surface friction
coefficient of the plate. Further, durability was evaluated from
the result of the measurement of the surface friction coefficient.
Conditions, such as the kinds of the copolymers, the contents of
the copolymers, and the solvents, and the results of the evaluation
are shown in Table 3 and Table 4 for the lubricity-imparting agents
used in Examples and Comparative Examples. In addition, a similar
evaluation was performed by using polyethylene terephthalate that
had not been subjected to any surface treatment, and the obtained
result was defined as Comparative Example 5.
<Surface Friction Coefficient>
The friction coefficient was measured with TRIBOGEAR (manufactured
by Shinto Scientific Co., Ltd.) under the conditions of a sliding
speed of 600 mm/min, a sliding distance of 50 mm, and a load of 10
g at room temperature in physiological saline while a contact
terminal made of stainless steel was brought into contact with the
plate.
<Durability>
The surface friction coefficient was measured by reciprocating the
contact terminal five times at one and the same place, and a case
in which the surface friction coefficient after the fifth
reciprocation increased by 25% or more as compared to the friction
coefficient after the first reciprocation was indicated by Symbol
"+", and a case in which the increase was less than 25% was
indicated by Symbol "++". In addition, a case in which the surface
friction coefficient showed a value close to that of Comparative
Example 5 at the time of the measurement on or before the fifth
reciprocation was indicated by Symbol ".times.".
TABLE-US-00001 TABLE 1 Polymerization Polymerization Polymerization
Polymerization Polymerizat- ion Example 1 Example 2 Example 3
Example 4 Example 5 Feed Monomer MPC 36.36 36.34 28.75 35.54 34.10
composition MBP 3.64 -- 4.32 0.40 3.84 of MHP -- 3.66 -- -- --
polymerization GMA -- -- -- -- -- of BMA -- -- 6.92 4.06 2.05
copolymer SMA -- -- -- -- -- (g) AzSt -- -- -- -- -- AEMA -- -- --
-- -- Additive ABA -- -- -- -- -- TEA -- -- -- -- -- Solvent EtOH
155.11 155.11 155.11 155.11 155.11 nPA -- -- -- -- -- PW -- -- --
-- -- Initiator AIBN 4.89 4.89 4.89 4.89 4.89 Total 200.00 200.00
200.00 200.00 200.00 Polymerization At 65.degree. C. At 65.degree.
C. At 65.degree. C. At 65.degree. C. At 60.degree. C. conditions
for 6 for 6 for 6 for 6 for 6 (polymerization hours hours hours
hours hours temperature and polymerization time) Composition
Constitutional MPC 90 90 60 80 80 ratio unit of (A) copolymer
Constitutional MBP 10 -- 10 1 10 (mol %) unit MHP -- 10 -- -- --
(B) GMA- -- -- -- -- -- Az AzSt -- -- -- -- -- Constitutional BMA
-- -- 30 19 10 unit SMA -- -- -- -- -- (C) Others AEMA -- -- -- --
-- Polymerization Water YES YES YES YES YES result solubility
Weight-average 132,000 106,000 118,000 145,000 520,000 molecular
weight (Symbol of P1 P2 P3 P4 P5 copolymer) Polymerization
Polymerization Polymerization Polymerization Polymerization Example
Example 6 Example 7 Example 8 Example 9 10 Feed Monomer MPC 32.78
28.57 31.84 39.81 39.01 composition MBP 7.02 -- 3.59 -- -- of MHP
-- 4.55 -- -- -- polymerization GMA -- -- -- 0.19 0.99 of BMA 0.20
6.88 -- -- -- copolymer SMA -- -- 4.57 -- -- (g) AzSt -- -- -- --
-- AEMA -- -- -- -- -- Additive ABA -- -- -- 0.33 1.70 TEA -- -- --
0.03 0.14 Solvent EtOH 155.11 155.11 155.11 -- -- nPA -- -- --
154.14 154.14 PW -- -- -- -- -- Initiator AIBN 4.89 4.89 4.89 5.86
5.86 Total 200.00 200.00 200.00 200.36 201.84 Polymerization At
65.degree. C. At 65.degree. C. At 65.degree. C. At 60.degree. C. At
60.degree. C. conditions for 6 for 6 for 6 for 4 for 4
(polymerization hours hours hours hours hours temperature and and
and polymerization then at then at time) 70.degree. C. 70.degree.
C. for 2 for 2 hours hours Composition Constitutional MPC 80 60 80
99 95 ratio unit of (A) copolymer Constitutional MBP 19 -- 10 -- --
(mol %) unit MHP -- 10 -- -- -- (B) GMA- -- -- -- 1 5 Az AzSt -- --
-- -- -- Constitutional BMA 1 30 -- -- -- unit SMA -- -- 10 -- --
(C) Others AEMA -- -- -- -- -- Polymerization Water YES YES YES YES
YES result solubility Weight-average 135,000 120,000 120,000
166,000 143,000 molecular weight (Symbol of P6 P7 P8 P9 P10
copolymer) Polymerization Polymerization Polymerization
Polymerization Example Example Example Example 11 12 13 14 Feed
Monomer MPC 35.70 30.28 35.70 35.70 composition MBP -- -- -- -- of
MHP -- -- -- -- polymerization GMA 4.30 2.43 4.08 2.15 of BMA --
7.29 0.21 2.15 copolymer SMA -- -- -- -- (g) AzSt -- -- -- -- AEMA
-- -- -- -- Additive ABA 7.39 4.18 7.02 3.70 TEA 0.61 0.35 0.58
0.31 Solvent EtOH -- -- -- -- nPA 154.14 154.14 154.14 154.14 PW --
-- -- -- Initiator AIBN 5.86 5.86 5.86 5.86 Total 208.00 204.53
207.60 204.00 Polymerization At 60.degree. C. At 60.degree. C. At
60.degree. C. At 60.degree. C. conditions for 4 for 4 for 4 for 4
(polymerization hours hours hours hours temperature and and and and
and polymerization then at then at then at then at time) 70.degree.
C. 70.degree. C. 70.degree. C. 70.degree. C. for 2 for 2 for 2 for
2 hours hours hours hours Composition Constitutional MPC 80 60 80
80 ratio unit of (A) copolymer Constitutional MBP -- -- -- -- (mol
%) unit MHP -- -- -- -- (B) GMA- 20 10 19 10 Az AzSt -- -- -- --
Constitutional BMA -- 30 1 10 unit SMA -- -- -- -- (C) Others AEMA
-- -- -- -- Polymerization Water YES YES YES YES result solubility
Weight-average 125,000 58,000 98,000 85,000 molecular weight
(Symbol of P11 P12 P13 P14 copolymer)
TABLE-US-00002 TABLE 2 Polymerization Polymerization Polymerization
Polymerization Polymerizat- ion Example Example Example Example
Example 15 16 17 18 19 Feed Monomer MPC 35.70 33.24 38.10 32.35
28.60 composition MBP -- -- -- -- -- of MHP -- -- -- -- --
polymerization GMA 0.21 2.00 -- -- -- of BMA 4.08 -- -- -- 6.89
copolymer SMA -- 4.76 -- -- -- (g) AzSt 3.79 15.30 9.02 AEMA -- --
-- -- -- Additive ABA 0.37 3.45 -- -- -- TEA 0.03 0.29 -- -- --
Solvent EtOH -- -- -- -- -- nPA 154.14 154.14 152.24 146.49 149.63
PW -- -- -- -- -- Initiator AIBN 5.86 5.86 5.86 5.86 5.86 Total
200.40 203.74 200.00 200.00 200.00 Polymerization conditions At
60.degree. C. At 60.degree. C. At 60.degree. C. At 60.degree. C. At
60.degree. C. (polymerization temperature for 4 for 4 for 4 for 4
for 4 and polymerization time) hours hours hours hours hours and
then and then and then and then and then at 70.degree. C. at
70.degree. C. at 70.degree. C. at 70.degree. C. at 70.degree. C.
for 2 for 2 for 2 for 2 for 2 hours hours hours hours hours
Composition Constitutional MPC 80 80 95 80 60 ratio of unit
copolymer (A) (mol %) Constitutional MBP -- -- -- -- -- unit MHP --
-- -- -- -- (B) GMA-Az 1 10 -- -- -- AzSt -- -- 5 20 10
Constitutional BMA 19 -- -- -- 30 unit SMA -- 10 -- -- -- (C)
Others AEMA -- -- -- -- -- Polymerization Water solubility YES YES
YES YES YES result Weight-average 66,000 55,000 72,000 63,000
25,000 molecular weight (Symbol of (co)polymer) P15 P16 P17 P18 P19
Polymerization Polymerization Polymerization Polymerization Example
Example Example Example 20 21 22 23 Feed Monomer MPC 32.50 34.80
35.52 31.70 composition MBP -- -- -- -- of MHP -- -- -- --
polymerization GMA -- -- -- -- of BMA 0.20 3.14 4.06 -- copolymer
SMA -- -- -- 4.55 (g) AzSt 14.60 4.11 0.84 7.50 AEMA -- -- -- --
Additive ABA -- -- -- -- TEA -- -- -- -- Solvent EtOH -- -- -- --
nPA 146.84 152.08 153.72 150.39 PW -- -- -- -- Initiator AIBN 5.86
5.86 5.86 5.86 Total 200.00 200.00 200.00 200.00 Polymerization
conditions At 60.degree. C. At 60.degree. C. At 60.degree. C. At
60.degree. C. (polymerization temperature for 4 for 4 for 4 for 4
and polymerization time) hours hours hours hours and then and then
and then and then at 70.degree. C. at 70.degree. C. at 70.degree.
C. at 70.degree. C. for 2 for 2 for 2 for 2 hours hours hours hours
Composition Constitutional MPC 80 80 80 80 ratio of unit copolymer
(A) (mol %) Constitutional MBP -- -- -- -- unit MHP -- -- -- -- (B)
GMA-Az -- -- -- -- AzSt 19 5 1 10 Constitutional BMA 1 15 19 --
unit SMA -- -- -- 10 (C) Others AEMA -- -- -- -- Polymerization
Water solubility YES YES YES YES result Weight-average 50,000
49,000 33,000 28,000 molecular weight (Symbol of (co)polymer) P20
P21 P22 P23 Comparative Comparative Comparative Comparative
Polymerization Polymerization Polymerization Polymerization Example
1 Example 2 Example 3 Example 4 Feed Monomer MPC 40.00 35.94 23.55
18.20 composition MBP -- -- -- -- of MHP -- -- -- -- polymerization
GMA -- -- -- -- of BMA -- 4.06 26.45 -- copolymer SMA -- -- -- --
(g) AzSt -- -- -- -- AEMA -- -- -- 1.20 Additive ABA -- -- -- --
TEA -- -- -- -- Solvent EtOH 155.11 155.11 70.90 -- nPA -- -- -- --
PW -- -- -- 80.00 Initiator AIBN 4.89 4.89 4.10 0.15 Total 200.00
200.00 125.00 99.65 Polymerization conditions At 65.degree. C. At
65.degree. C. At 55.degree. C. At 60.degree. C. (polymerization
temperature for 6 for 6 for 24 for 8 and polymerization time) hours
hours hours hours Composition Constitutional MPC 100 81 30 90 ratio
of unit copolymer (A) (mol %) Constitutional MBP -- -- -- -- unit
MHP -- -- -- -- (B) GMA-Az -- -- -- -- AzSt Constitutional BMA --
19 70 -- unit SMA -- -- -- -- (C) Others AEMA -- -- -- 10
Polymerization Water solubility YES YES NO YES result
Weight-average 188,000 138,000 600,000 800,000 molecular weight
(Symbol of (co)polymer) Q1 Q2 Q3 Q4
TABLE-US-00003 TABLE 3 Example 1 Example 2 Example 3 Example 4
Example 5 Example 6 Example 7 Kind of copolymer used P1 P2 P3 P4 P5
P6 P7 Ratio of copolymer used (%) 100 100 100 100 100 100 100 Other
component: ratio of MPC -- -- -- -- -- -- -- (%) Kind of solvent
EtOH EtOH EtOH EtOH EtOH EtOH EtOH Friction At 0.101 0.071 0.081
0.087 0.054 0.075 0.062 coefficient concentration of 1.0 mass % At
0.098 0.092 0.079 0.074 0.062 0.074 0.069 concentration of 0.5 mass
% At 0.095 0.103 0.095 0.091 0.061 0.082 0.085 concentration of 0.1
mass % Durability At ++ ++ ++ + ++ ++ ++ concentration of 1.0 mass
% At ++ ++ ++ + ++ ++ ++ concentration of 0.5 mass % At + + + + + +
+ concentration of 0.1 mass % Example Example Example Example
Example Example 8 Example 9 10 11 12 13 14 Kind of copolymer used
P8 P9 P10 P11 P12 P13 P14 Ratio of copolymer used (%) 100 100 100
100 100 100 100 Other component: ratio of MPC -- -- -- -- -- -- --
(%) Kind of solvent EtOH EtOH EtOH EtOH EtOH EtOH EtOH Friction At
0.025 0.019 0.017 0.017 0.018 0.014 0.009 coefficient concentration
of 1.0 mass % At 0.031 0.017 0.014 0.014 0.014 0.017 0.012
concentration of 0.5 mass % At 0.03 0.028 0.025 0.021 0.029 0.02
0.018 concentration of 0.1 mass % Durability At ++ ++ ++ ++ ++ ++
++ concentration of 1.0 mass % At ++ ++ ++ ++ ++ ++ ++
concentration of 0.5 mass % At + + + + ++ + + concentration of 0.1
mass %
TABLE-US-00004 TABLE 4 Example Example Example Example Example
Example Example Example Example 15 16 17 18 19 20 21 22 23 Kind of
copolymer used P15 P16 P17 P18 P19 P20 P21 P22 P23 Ratio of
copolymer used 100 100 100 100 100 100 100 100 100 (%) Other
component: ratio of -- -- -- -- -- -- -- -- -- MPC (%) Kind of
solvent EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH Friction At
0.01 0.008 0.018 0.021 0.012 0.007 0.009 0.014 0.017 coefficient
concentration of 1.0 mass % At 0.008 0.012 0.015 0.023 0.009 0.012
0.012 0.011 0.011 concentration of 0.5 mass % At 0.018 0.031 0.027
0.04 0.011 0.011 0.015 0.021 0.019 concentration of 0.1 mass %
Durability At ++ ++ ++ ++ ++ ++ ++ ++ ++ concentration of 1.0 mass
% At ++ ++ ++ ++ ++ ++ ++ ++ ++ concentration of 0.5 mass % At + ++
+ + ++ + ++ + ++ concentration of 0.1 mass % Example Example
Example Comparative Comparative Comparative Comparative C-
omparative 24 25 26 Example 1 Example 2 Example 3 Example 4 Example
5 Kind of copolymer used P2 P12 P20 Q1 Q2 Q3 Q4 -- Ratio of
copolymer used 50 50 50 100 100 100 100 -- (%) Other component:
ratio of 50 50 50 -- -- -- -- -- MPC (%) Kind of solvent EtOH/PW
EtOH/PW EtOH/PW EtOH EtOH EtOH EtOH EtOH Friction At - - - 0.189
0.201 0.072 0.194 0.194 coefficient concentration (free of 1.0 of
mass % copolymer) At 0.008 0.006 0.005 - - - - concentration of 0.5
mass % At 0.006 - - - - - - concentration of 0.1 mass % Durability
At - - - x x x x x concentration of 1.0 mass % At ++ ++ ++ - - - -
concentration of 0.5 mass % At ++ - - - - - - concentration of 0.1
mass %
As is apparent from the results of Table 3 and Table 4, the
friction coefficient of a substrate surface was able to be reduced
by: coating the substrate surface with a lubricity-imparting agent
including a copolymer containing a constitutional unit based on
2-methacryloyloxyethyl phosphorylcholine and a constitutional unit
based on a photoreactive functional group-containing monomer, or a
copolymer containing a constitutional unit based on
2-methacryloyloxyethyl phosphorylcholine, a constitutional unit
based on a photoreactive functional group-containing monomer, and a
constitutional unit based on a hydrophobic group-containing
monomer; and irradiating the substrate surface with light. In
addition, the friction coefficient maintained a low friction
coefficient even after the 5-reciprocation measurement.
Meanwhile, as can be seen from the results of Table 4, in each of
Comparative Example 1 (in which the substrate surface was coated
with the polymer formed only of the constitutional unit based on
2-methacryloyloxyethyl phosphorylcholine), Comparative Example 2
(in which the substrate surface was coated with the water-soluble
copolymer that had only the constitutional unit based on
2-methacryloyloxyethyl phosphorylcholine and the constitutional
unit based on a hydrophobic group-containing monomer, and was free
of any constitutional unit based on a photoreactive functional
group-containing monomer), and Comparative Example 4 (in which the
substrate surface was coated with the copolymer that was free of
any constitutional unit based on a hydrophobic group-containing
monomer and any constitutional unit based on a photoreactive
functional group-containing monomer, but had the constitutional
unit based on 2-methacryloyloxyethyl phosphorylcholine and the
constitutional unit having an amino group), no reduction in
friction coefficient was observed because no copolymer layer was
formed on the substrate surface by the photoirradiation, and hence
the value of the friction coefficient was comparable to that of
Comparative Example 5 (polyethylene terephthalate that had not been
subjected to any surface treatment). In addition, it was revealed
that in Comparative Example 3 (in which the substrate surface was
coated with the water-insoluble copolymer that had only the
constitutional unit based on 2-methacryloyloxyethyl
phosphorylcholine and the constitutional unit based on a
hydrophobic group-containing monomer, and was free of any
constitutional unit based on a photoreactive functional
group-containing monomer), the friction coefficient in the first
measurement was able to be reduced because the copolymer was
water-insoluble, but as the measurement was repeated, the value of
the friction coefficient increased, in other words, the friction
coefficient was deficient in durability.
It was confirmed from the foregoing results that the
lubricity-imparting agent of the present invention was able to
impart durable lubricity to a substrate surface through the coating
of the substrate surface with the agent and the irradiation of the
substrate surface with light.
INDUSTRIAL APPLICABILITY
The lubricity-imparting agent of the present invention can impart
durable lubricity to a substrate surface. In addition, the article
of the present invention has highly durable lubricity.
* * * * *